Grease composition



Patented Sept. 15, 1953 UNITED STATES PATENT OFFICE Berkeley, ment Company, ration of Delaware Galif., assi gnors to Shell Develop- San Francisco, Calif., a corpo- No Drawing. Application August 15, 1950, Serial No. 179,630

17 Claims.

This invention relates to improved lubricating grease compositions. More particularly, this invention pertains to improved grease compositions which are capable of resisting oxidation under both static and dynamic conditions, bleeding, age-hardening and possess outstanding mechanical stability and are thermally reversible.

It is well established that oxidation has a profound deteriorating efiect upon lubricants and lubricating compositions. The rapidity of this deterioration varies with diiierent lubricants and depends in part upon the source of the base oil, the presence of additives therein as well as on the conditions to which the lubricant is exposed. Once oxidation has started in a lubricant, the deterioration caused thereby appears to be an autocatalytic phenomenon which results in further deterioration of the lubricant.

A general deficiency encountered in greases is their lack of resistance to shear as well as other types of mechanical forces which are generally exerted upon greases under various working conditions. Thus, in the lubrication of ball and roller bearings, greases are often subjected to temperatures in excess of 250 to 300 which temperatures accelerate oxidation, and coupled with high shearing stresses, the greases break down in structure and are incapable of adhering to the lubricating surfaces, resulting in bearing corrosion, wear and failure. It is essential of good greases, therefore, to resist shearing stresses and oxidation, particularly over wide temperature ranges.

The cause or causes of age-hardening of greases at present is not understood. It is believed to be caused by the soap fibers which in storage tend to form cross layers due to the presence of an active group associated with the soap micelles, and thereby increases the consistency of the grease. Such hardening is extremely undesirable for it introduces numerous lubricating difficulties such as in pumping equipment and the like.

Bleeding is another phenomenon which is frequently encountered in grease compositions. Bleeding is primarily due to the fact that the soaps present in grease compositions have a marked tendency to synerize, thereby causing a separation of th soap from the oil or synthetic base lubricant in which it is dispersed.

Generally, to inhibit bleeding and improve the texture of greases special precautionary measures are taken, such as employing slow or rapid means of cooling, or extensively working the grease in special homogenizers, e. g., the Cornell homogenizerand the like. Such procedures are msuaHy im -co u i g and add to the cost of the greases. Other ways of producing stable, non-bleeding greases have been attempted by either reducing the soap content generally to less than about 5% by weight or by increasing the soap content to a maximum. These methods of stabilizing greases against bleeding have also proved to be unsatisfactory because in the case of reducing the soap content to less than 5% such reases become limited in their use due to the low soap content, while increasing the soap content to a maximum makes the grease too clostly and such products generally possess an. undesired consistency.

It is an object of this invention to produce rease compositions having outstanding mechanical stability under dynamic and static conditions. It is another object of this invention to produce greases having good thermal reversibility and which are capable of resisting shearing stresses over wide temperature ranges. Still another object of this invention is to produce nonbleeding greases. Still another object of this invention is to produce novel greases of this invention by conventional grease-making techniques either by batch or continuous processes. Furthermore, it is an object of this invention to produce a multi-purpose grease of outstanding lubrieating properties.

These and other objects of this invention will be apparent from the following description and the appended claims.

Broadly stated, this invention comprises a lubricating grease composition containing in addition to the lubricating oil and gel-forming agent, a combination of two, and preferably three, particular types of additives in amounts much less than that of the gelling agent used to form the grease. The combination of additives produces a synergistic effect resulting in a grease composition possessing the properties enumerated above and exhibiting in particular outstanding and unexpected resistance to oxidation. The two additives present in combination are (1) a high molecular weight naphthyl amine and (2) a reaction product of a phosphorus sulfide with a dicyclic terpene. Still better results are obtained both from corrosion and oxidation standpoints if to this combination is also added a metallic salt of carbamic acid or its analogs, represented by the formula:

wherein R1 and R2 can be hydrogen and/or an The primary oxidation inhibitors contemplated herein are phosphorusand- 1.sulfur containing reaction products obtained byreacti'on', at a tem perature of above about 106 C., of .aphosphorus: I

sulfide and a dicyclic terpene or a material predominantly comprised ci a dicyclic terpene.

All of the phosphorus sulfides, such as PSti-(or:

PS2), P4S6 (Or Pass), P2S5, P4S7, P4810, etc., are

contemplated as reactants in the preparation-of primary oxidation inhibitors, but Pass is particularly preferred; As usedherein; the designation: dicyclic terpene refersto thoseterpenes which. are characterized :by the presence of one double.

bond in the molecule-and: are .built up of: two ringv systems.

resentative of 'Which'materials are the essentialor volatile oils, which are predominantly c-omprised of such a terpene or terpenes and are typi fied by turpentine oil, the majorconstituent of which is pinene. Particular 1 preference is accorded to pinene and turpentineoil;

It is to be undertsood-that the aforesaid designation, dicyclic terpene,. is not inclusive of such" terpenes as those known in the'art as monocyclic terpenes, which are typified; by dipentene and terpinolene. It is also tobe understood that the. dicyclic terpenes should 'not beconfused with the olefin hydrocarbon terpenes such as myrcene.

Although a complete understanding of the chemical composition of the reaction products of phosphorus sulfideand di'cyclic terpenes has not" been achieved at this time; a partial understand ing of their composition' 'may be-obtainedby'noting the characteristics involved in 'thereaction. For example, the reaction of phosphorus pentasulfide and pinene commences at about 100 C. and is exothermic in nature. During the reaction, the

reaction mixtureincreases appreciably in Viscosity and little, if any, hydrogen sulfide is evolved therefrom. The reaction product obtained .con-

tains phosphorus and sulfurin. substantially the same amounts as in the particular phosphorus sulfide reacted with the pinene. It'Woul'd'therefore appear that the reaction is one of :addition; that is, addition of phosphorus sulfideto the one I unsaturated bondl present "in pinene.

Although thereaction temperature for the reaction described above .shouldb'e one .of at least about .100? C., the preferreditemperatures fall within the range-of about 100 C. to about 160 C;-

or higher.

The proportions-of reagentsused intheprep-J aration of the primary oxidation inhibitors may be varied in order to prepare. reaction. products having different degrees of oil-solubility.- In this regard, it is preferred that about one mol of phosphorus sulfide be reacted with four mols of a dicyclic terpene in order -to obtain a reaction product relatively soluble in petroleum oils. For example, when more than one mol of PzSs is used with .3e5-mols .ofpinene,. a viscous gel-lik reac- Illustrative of such: compounds 1 are pinene, campheneiand fenchenee Also contem-- plated as coming Withln'this particular designation are those materials which are predominantly comprised of one or'more dicyclic .terpenes, rep-- tion product is obtained, and this product is definltely insoluble in petroleum oils. When less than one mol of PzSs is used with 3-5 mols of pinene, a viscous oil also somewhat insoluble in mineral oil is obtained, after the unreacted pinene .has beenremoved by, distillation. Accordingly, it is to be understood that although effective primary oxidation inhibitors can be obtained by using different ratios of reactants, particularly preferred inhibitors are those obtained by using approximately one mol of a phosphorus sulfide for about 3.5 to- 4=.5 mols of a dicyclic terpene, while :the-.most-.suitable ratio is 1 mol P2S5 to 4 mols terpene.

There-:is;1however,- still another desirable procedure for preparing the primary oxidation inhibitor. ln order'to obtain a relatively nonvis'cousreaction product, the dicyclic terpene, such-as .pinene, may be blended with a comparatively inert solvent, such as petroleum oil, and thenv treatedas.describedabove to vyieldan oil blendlof the reaction product. The preferred procedure .of .thisfllatter type involves the useof" a 1:1 blend .of Idi'cycliclterpene and petroleum oil with the phosphorussulfide, .the molar ratio of said terpeneto saidIsulfide being about 3 :1 to .511.

When. usedinyiscous.mineral toil fractions in small amounts, .the. aforesaid Iprimary oxidation inhibitors effect improvementof several of the cxidation characteristics thereof by, preventing, for example, corrosion of hard metal bearings, by inhibition ofacid formation, by inhibition of for-.-

mation of gummy deposits :in' engines, bypree venting increase :in viscosity;- etc..

The organic" amines The aromatic amines maybe either monocyclic or polycyclic. The-naphthyl amine include pri-.'

mary, secondary or tertiary alkyl, aryl or .aralkyl amines such. as. phenylsalphaenaphthyl amine,

phenyl-beta-naphthylamine, tetraline naphthylamine, alpha,a1pha-., ,alpha-beta or beta,beta.

dinaphthylamines; benzyl phenyl naphthylamineand diphenyl naphthylamine.

The amount of :both; the amine or theterpene reaction product which .canberadded, to grease comp-ositionsof this invention depends upon-various factors, suchassthelubricating base used to. form the grease; the amount-and typeof soap or;

inorganic-gelling :agent. and: the like..- Generally, the amines areeused: in :amounts :varying from 131% to 5% andzpreferably froma25% -.to-2%. The-- phosphorus sulfide-terpene reaction products-are-- also to-be .usedin like amount'sr: Depending upon the typetof grease-produced; the. ratio of the :two additives icanv vary: over wide llimits; preferably.

of from: one :part: amine andcfive iparts terpene reactionproductto five parts'amineand one =part terpene reactionfproduct:

Theigelling "agent The gelling agent used to formthe grease may myristoleic acids, cottonseedoil fatty acid, palm 1 oil fatty acids,.1inoleic,ihydrogenatedfish oil fatty acids, palmitolic, oleic, linoleic, ricinoleic, erucic acids and their mixtures and/or their glycerides,

such aslard, beef, rapeseed, palm, menhaden, herring. oils, etc. Other acids may be included among which are: acids produced by oxidation of petroleum oil andwaxes, rosin. acids, tall oil acids, abietic acids, naphthenlc acids, petroleum sulfonic acids and the like.

A particularly preferred class of saponifiable materials is the hydroxy fatty acids and their glycerides, such as: dimethyl hydroxy caprylic acid, dimethyl hydroxy capric acid, 12-hydroxy stearic acid, 9,10-dihydroxy-stearic acid, hydroxy palmitic acid, ricinoleic acid, ricinelaidic acid, dihydroxy behenic acid and the like. The preferred hydroxy fatty acids are those in which the hydroxy group is at least 12 carbon atoms removed from the carboxyl group. Also, it is preferable to use hydroxy fatty acids having at least 12 carbon atoms and up to about 32 carbonatoms and preferably those having between 14 and 32 carbon atoms in the molecule. Instead of using the free fatty acids containing a hydroxy radical, their glycerides can be used such as castor oil, or hydrogenated castor oil or mixtures of free hydroxy fatty acids and their glycerides can be used. Mixtures of hydroxy and non-hydroxy fatty acids can be used to form soap.

The saponifying agent used to make the soap may be any oxide or hydroxide of one or several of metals selected from groups I, II, III, VI, VII, and VIII. Specifically, the cation portion of the soaps may be Na, K, Li, Cs, Ca, Sr, Ba, Cd, Zn, Al, Pb and Co. Mixtures of soaps can be used, and the soap can be made in situ or premade soaps can be used to form the grease. Specific examples of preferred soaps or mixtures thereof are: lithium stearate, lithium 12-hydroxy stearate, lithium castorate, lithium soap of hydrogenated fish oil fatty acids, lithium soap of mixed stearic and hydroxy stearic acid, sodium stearate, sodium hydroxy stearate, sodium oleate, potassium oleate, potassium rosinate, calcium stearate, calcium hydroxy stearate, aluminum stearate, aluminum soap of fish oil fatty acids, barium hydroxy stearate, barium stearate, sodium soap of mixed stearic and hydroxy stearic acids, lithium soap of mixed oleic and hydroxy stearic acid, aluminum castorate, mixed soaps of lithium stearate and sodium stearate, mixed soaps of lithium hydroxy stearate and sodium stearate, mixed soaps of lithium hydroxy stearate and calcium stearate, etc.

In addition to greases gelled by the presence of soaps, greases thickened or gelled by the presence of inorganic colloids may be utilized as the base composition containing the combination of additives of the present invention. In particular, the inorganic colloidal materials useful for this purpose include the inorganic oxides and hydroxides of alkali metals, alkaline earth metals, silica, and combinations of the same. Silica greases, for example, may be prepared either by incorporating a silica aerogel in a suitable lubricant or by transferring an unshrunken gel from the medium in which it is originally formed either directly or indirectly into the lubricating medium. The latter process specifically contemplates the formation of a hydrogel such as silica hydrogel, addition of a hydrophobic surface-active agent, and incorporation of the compositions so formed with lubricating oil followed by elimination of water and homogenizing the grease so formed.

Another suitable method for the preparation of such greases comprises utilizing the ion-exchange capacity of naturally occurring or synthetic zeolites and swelling-type clays such as bentonite to form gelling agents bearing hydrophobic radicals. A specific instance of this comprises forming a hydrosol of hectorite (a magnesium bentonite), adding thereto a quaternary ammonium salt such as dimethyl dioctadecyl ammonium chloride to cause the formation of a hydrogel of the amino clay products; incorporating the hydrogel in mineral oil and eliminating water therefrom by distillation. Other suitable inorganic colloiding agents include especially, alumina, magnesia, lime, copper sulfide, and similar inorganic substances capable of colloid formation.

The content of gelling agent in grease compositions of this invention may vary over wide limits and may be as high as 50% by weight of the total grease. In practice, grease compositions containing soaps, normally comprise from 5% to 35% by weight of soap, while in the case of greases gelled with inorganic colloids the latter is normally present in amounts from about 2% to about 20% by weight.

Lubricating oil bases The grease-forming lubricant bases used in preparing the greases of the present invention may vary widely in character and include mineral oil of wide viscosity, the range varying from about 150 SUS at F. to about 2000 SUS at 100 F. The viscosity index of the oil can vary from below zero to about 100 and have an average molecular weight ranging from about 250 to about 600. It may be highly refined and solvent treated, if desired, by any known means. A preferred mineral oil is one which has a viscosity of 300 to 700 SUS at 100 F., or a viscosity of 65 to 100 SUS at 210 F. and a viscosity index of from 40 to 70 and an average molecular weight of 350 to 750. Instead of using straight mineral oil as the base, synthetic oils and lubricants may be substituted in part or wholly for the mineral oil. Among the synthetic lubricants which can be used are: polymerized olefins; copolymers of alkylene glycols and alkylene oxides; organic esters, e. g., Z-ethylhexyl sebacate dioctyl phthalate, trioctyl phosphate; polymeric tetrahydrofuran; polyalkyl silicone polymers, e. g., dimethyl silicone polymer, etc. Under some conditions of lubrication, minor amounts of a natural animal or vegetable oil such as oastor oil, lard oil, etc., may be admixed with the hydrocarbon oil and/or synthetic oil used in making grease compositions of this invention.

In addition to the essential combination of ingredients described hereinbefore, a further improvement may be made in the grease compositions by the addition thereto of the metallic salts of carbamic acid or its analogs. This class of materials is represented by the general formula:

which can be exemplified by such specific compounds as:

Ca, Ba, Na, Zn, Cu, Ni, salts of dibutyl monoand dithiocarbamic acid Na, Ca, Zn, Cu, Ni, salts of diethyl monoand dithiocarbamic acid Na, Ca, Zn, Cu, Ni, Co salts of diamyl monoand dithiocarbamic acid Na, Ca, Zn, Cu, Ni, Co salts of dihexyl monoand dithiocarbamic acid Na, Ca, Zn salts of dioctyl monoand dithiocarbamic acid I Ca, Zn, Cu, Ni salts of N-ethyl-N-phenyl mono and dithiocarbamic acid wherein R1 and R2 are hydrogen atoms or Oi1-' solubilizing organic radicals such as normal-alkyl, isoalkyl, alicyclic, aryl, 'aralkyl, alkaryl and/or heterocyclic groups. X1 and X2 are oxygen, sulfur, selenium or tellurium; and M is a metallic 8 vention are madeit is preferred that they be cooled uniformly and rapidly either in tubes of small diameter or in their layers by feeding the hot grease onto a steel belt and subjecting the radical. grease to a current of air or other cooling medium so as to cool the grease in a uniform fashion sa 1 hex l onoand gf ggg gi g dlcyc O y m free from shearing stresses. The primary additives and if desired the secondary additives can Z s s m noc t l m noand d1th1ocar- 353 i 0 e y o be added to the grease at any convenient time. Z C N, It i (cat 1 h 1) m 0 and 10 A preferred time for adding the additives of this 1 5a p on invention is while the grease is in a hot liquid d1th1ocarbam1c acid state L1 2 dlbenzyl monoand dlthlocar The following table illustrates specific grease bam1c acid compositions of this invention, each component Zn and N1 salts of d1(amy1 plp rldyl mOIlO- and of which may be used in the range indicated dithiocarbamic acid above in the general formulations.

Components 1 2 3 4 5 6 7 8 9 10 ll 12 13 Soaps:

Alrlcinoleate x x i Li-l2-hydroxy stearate. x Li soaps of hydrogenated fish x Sodium stearate x Ca stearate x .i. Ba Stearate x Li stearate i x x x Amines:

Phenylalpha-naphthylamine. x x x x x x x Phenylenediainine x x x Phenylbeta-naphthylamine x x l x i Condensation Products:

Pincus-P285 x x x x x x Turpentine-P285" x x x Dipentene-Pzss x x x Oarbamates:

Zndibutyldithiocarbamate x x x x Ga dihexyl dithiocarbamate x u- Zn dicyclohexyl dithiocarbamate x Lubricating Oils:

Mineraloil x x x x x x x x x x Di-(z-ethylhexyl) sebacate x x i x Zn, Ca, Na salts of dihexyl monoand diseleno carbamic acid Zn salt of dicyclohexyl monoand diselenocarbamic acid Na, Zn, Ni, Cu salts of dibutyl carbamic acid Na, Ca, Zn salts of dihexyl carbamic acid Ca and Zn salts of dicyclohexyl carbamic acid C0 salts of monocetyl carbamic acid Zn salts of dibenzyl carbamic acid.

The preferred class of the above materials comprises the metallic salts of dialkyl dithiocarbamic acid, and specifically the zinc salts of dialkyl dithiocarbamic acids, wherein the alkyl radicals each contain from about 2 to about 12 carbon atoms. These carbamates may be present in amounts from about .01% to 2% and preferably from .1% to 1% by weight based on the total composition.

Greases of this invention may be made by conventional or special methods and either by the batch or continuous process. In the case of lithium soap grease made by the conventional method, a calculated amount of lithium soap of between about 5 and or higher is charged into a suitable grease kettle together with about half of the required amount of oil. The oil-soap mixture is heated to around about 350 to 450 F. under agitation until a homogeneous mass is obtained. The balance of the oil is then slowly added with stirring. Stirring is continued until a homogenous mass is formed at which point the grease is allowed to cool either in the grease kettle or in pans to the ambient temperature. The grease thus formed is generally lumpy and requires reworking by milling or homogenizing to produce a smooth and relatively stable grease. If soda soap or alkaline earth greases are made, they may be cooled slowly in the kettle, whereas if lithium or aluminum soap greases of this in- Ogygen a sor Sample Additive, percent wt. tion s 1,500 cc A None 2. 7 B 0.25% phenyl alphanaplithylamine 15.5 C 1.5% Past-turpentine reaction product 78.9 D 0.25% phenyl alpl1a napththylamine+0.5% 62.7

Zn dibutyl dithio carbamate. E 0.25% phenyl alphanaphthylamine+1.5% 138 Past-turpentine reaction product. F 0.25% phenyl alphanaphthylamine+l.5%

Bass-turpentine reaction product+0.5% Zn dibutyl dithiocarbamate.

Minor amounts of secondary additives can be admixed with greases of this invention such as extreme pressure agents and can be added to such greases and the preferred comprise esters of phosphorus acids such as triaryl, alkylhydroxy, aryl, or aralkyl phosphates, thiophosphates, or phosphites, etc., neutral aromatic sulfur compounds such as diaryl sulfides and. polysulfides, e. g., diphenyl sulfide, dicresol sulfide, dibenzyl sulfide, methyl butyl diphenyl sulfide, etc., diphenyl selenide and diselenide; dicresol selenide and polyselenide, etc., sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e. g., sperm oil, Jojoba oil, etc. in which the sulfur is tightly bound; sulfurized long-chain olefins obtained by dehydrogenation or cracking of Wax; sulfurized phosphorized fatty acids, oils, esters and ketones, phosphorus acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorus acids with hydroxy fatty acids; chlorinated hydrocarbons such as chlorinated p-arafiins, aromatic hydrocarbons, terpenes, mineral lubricating oils, etc., or chlorinated esters of fatty acids containing the ch1orine in positions other than alpha position.

Additional ingredients which can be added are anti-wear agents such as oil-soluble salts of alkylphenol aldehyde condensation products, e. g., Ca octyl phenol-formaldehyde condensation product Ca diwax phenol sulfide, urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc.; or rubber, polyisobutylene, polyvinyl esters, esters of fatty acids, e. g., butyl stearate, etc, VI improvers such as polyisobutylene having a molecular weight above about 800, voltolized parafiin wax, unsaturated polymerized esters of fatty acids and monohydric alcohols, etc.; anti-oxidants, e. g., alkyl phenols, oiliness agents such as stearic and oleic acids and pour point depressors such as chlorinated naphthalene to further lower the pour point of the lubricant.

Example I The following composition represents a high temperature anti-friction bearing grease:

Per cent Sodium soaps of 25.0

Hydrogenated castor oil 10% Stearic acid 40% Beef tallow fatty acids 50% Phenyl alpha-naphthylamine 0.5

Pass-turpentine condensation product 1.5

Medium VI lubricating oil 73 This composition had an ASTM worked penetration of 287 and an average high temperature performance (Army/Navy specification AN G-a method) of 316 hours.

Example II A soda-base grease was prepared containing the following ingredients, the grease being stabilized with the combination of the recited additives.

High temperature performance at 10,000 R. P. M. and 300 F.time to failure in hours Oxidation (Norma Hofiman) Pressure drop at 100 hours p. s. i 3 Pressure drop at 500 hours p. s. i 11 10 Example III A lithium hydroxy fatty acid grease was prepared using the following components:

High V. I. lubricating oil, SSU at 100 F 50.65 High V. I. lubricating oil, 250 SSU at 100 F- 36.76

The above grease had the following properties:

Unworlred penetration at 77 F 255 Worked penetration 500 strokes 275 Dropping point, F 386 High temperature performance at 10,000 E. P. M. and 250 F.-time to failure in hours longer than 1900 Example IV The following grease was prepared using hydrogenated castor oil fatty acids instead of the hydrogenated castor oil as in Example III.

Percent Hydrogenated castor oil fatty acids 6.95 Lithium hydroxide monohydrate 1.0 Phenyl alpha-naphthylamine .25 Pass-turpentine reaction product 1.0

Zinc dibutyl dithiocarbamate .5

Tributyl phosphite .25 High V. I. lubricating oil 100 SSU at 100 F- 52.23 High V. I. lubricating oil 250 SSU at 100 F- 37.82

The following properties were obtained on the above grease:

Unworked penetration at 77 F Worked penetration 500 strokes 250 302 Dropping point, "F 386 High temperature performance at 10,000 R. P. M. and 250 F.-time to failure in hours 985 The invention claimed is:

1. A grease composition comprising the follow- 1ng ingredients:

Percent Lubricating oil, 100-250 SSU at 100 F 87.5

Phenyl alpha-naphthylamine .25 Pass-turpentine reaction product 1.0 Zinc dibutyl dithiocarbamate 0.5 Tributyl phosphite 0.25 Lithium soap of hydrogenated castor oil acids Balance 2. A grease composition comprising the followmg ingredients:

Percent Sodium soap of higher fatty acids 30.0 Lubricating oil 68.0 Phenyl alpha-naphthylamine 0.5 Pass-turpentine reaction product 1.0 Zinc dibutyl dithiocarbamate 0.5

' naphthyl amine grease of a sodium soap and minor amounts at least .0 1% "by weight each; suflicient to stabilize said grease ofphenyl alpha-naphthylamine and :the reaction product of phosphorus pentasulfide and turpentine.

' 5. -A-grease composition comprising a major a'mount of-a lubricating oil havin incorporated therein an amount suificientto ior-m a'grease'of ai -gelling-agent' and-0.01 to-5'% each of an aro- -maticnaphthyl amine and the reaction product of phosphorus pentas'ulfide and a=dicyclic terpene.

- 6. -A grease composition comprising a major ,amountof a lubricating oil having incorporated therein an amount suflicient to form a grease of -agelling agent and-minor amounts at least 0.01% "by weight each; sufiicient to stabilize said grease -of a naphthylamine and'a reaction product of turpentine and a phosphorus sulfide.

7 A grease composition comprising a major --amount of a lubricating-oil having incorporated therein an amount, sufficient to form a grease of a gelling agent and minor amounts at-least 0.01%

by weight each, sufficient to' stabilize said grease of an aromatic "naphthyl amine and a phosphorusand sulfur-containing reaction product obtained by reaction of a dicyclic terpene and a ahosphorus sulfide.

i8. A..grease composition-comprising a -major amount oia. lubricating oil having incorporated therein. anamount sufiicient to form a grease of colloidal.silicaandlminor amounts at least 0.01%

:by weight .each sumcient. to stabiliz said grease of a naphthylaamine anda phosphorus-and sulfur-containing reaction product obtained by reaction ofa dicyclic terpene and a phosphorus sul- "fide.

9. A grease composition comprising a major I amountera-lubricating oilhaving incorporated therein an-amount su'fiicienttoform a grease of i colloidal siliceous gelling agent and -minor amounts at -least0-.0l-% by=-weight each, sufficient to st'abilizesaid grease of a naphthyl amine and "a phosphor-us- --and --sulfurcontaining reaction product obtained by reaction of a dicyclic ter- Feneanda hPS hQIT-J- 'WmQ '10. Agrease composition comprisinga major amount of a lubricating oil having incorporated therein an amount sufficient to form a grease ofan inorganic 'c'olloidalgelling agent and minor to" stabilizesaid grease of a naphthyl amine and --a phosphor-usand I sulfur-containing reaction product obtained-by reaction-of 1 a dicyclic terpene and a phosphorussulfide.

"11. -A'grease composition comprising a major amount :of,-alubricating oil. having incorporated therein anarnount suificient to form a-grease of sodium soap and minor amounts at least 0.01%

",by weight each,.sufiicient.;tostabilize said grease of a naphthyl :amine and a phosphorusand sulfur-containin .reactionproduct obtained by reaction of a dicyclic terpene-and a phosphorus sulfide.

12. A grease composition comprising a major amount of a" lubricating oil having incorporated 'therein anamount-sufficient to form a' grease of 'a soap and "minor "amounts at least 0.01%by weight'ea'ch, sufficient to stabilize said grease'of-a and a phosphorusand sulfurcontaining reaction product obtained by reaction a 'dicyclicterpene and aphosporus sulfide.

. If '13. .A ,grease composition comprising major amount of a minerallubrica'ting oil having incorpor'ated therein. and amount siifii'cient to' form a grease ofv a gelling agent and minor, amountsjat least 0.01%.by5weight feach,.sufiicient,to"st.abilize said grease'of a naphthyl amine and phos- ,.phorusand. sulfur-containing reaction. product obtained by reaction of a dicyclic terpeneiarid a phosphorus sulfide.

14. A- grease compositioncomprising alfmajfor amount or" a lubricating .oilhaving incorporated therein an amount sufficient to form a greaseof a. gelling agent andminor amounts 'at 1east'0lOl% by weight each, sufficient to stabilizesaid greasejof anaphth'yl amine and a phosphor-use -a'nd sulfurcontaining reaction-product obtained-by, reaction of-a .dicyclic'..terpene .and aphosphorus' sulfide,

and ametal salt 'of an organic acid represented by. the formula: 7

wherein R1 and Ragare; selected from the, group consisting-of hydrogen, alkyl, alicyclic," aryl, aralkyl, alkaryl and-heterocyclic radicals-and X15 and X2 are elements of the group consisting-oioxygen, sulfur, selenium and tellurium.

15. A grease comr'iosition comprising a major amount of a lubricating oil having incorporated therein an. amount. sufficient toffo'rm" aj'gr'ea's'e of a gelling agent and minor amounts at 'l'ea'st0l01"% by weight each, sufficient to stabilize said grease oi a naphthyl amine and a phosphorusand; sulfur-containing.reaction.product obtained-my reactionsof .a .dicyclic ,terpene and ,a :gphosphorus sulfide,=.-and a metal :salt-of 'ajcarbarnic acid.

16... A. grease. composition; comprising a ma'jor amount of. .a glubricatingroil having: incorporated therein .an. amount. suificient:-to-- fo m' a grease pf a gelling agent andminor amounts at least 0.01%

by weight each; sufiicient to' stabilize=-said grease or I anaphthyl airii-neand a phosphorusand sulfur-'containing reaction prdductobtamedbyreaction of a dicyclic terpene and a phosphorus-sulfide, and a zinc salt of a oarbamic acid.

17. A grease composition-comprising a major amount.ci ar-lubricating oil having. incorporated therein. amount sufiicient ..-to 1 form ,-a-' grease of a gelli-ng agent and-minor; amounts atleast 0.01% by Weight each, sufficient to stabilize said :greaseof a naphthyl amine and a phosphorusfand suliur-containing reaction -product obtained by reaction of a dicyclic terpene and a phosphorus References Citd in" the file of this patent 

5. A GREASE COMPOSITION COMPRISING A MAJOR AMOUNT OF A LUBRICATING OIL HAVING INCORPORATED THERIN AN AMOUNT SUFFICIENT TO FORM A GREASE OF A GELLING AGENT AND 0.01 TO 5% EACH OF AN AROMATIC NAPHTHYL AMINE AND THE REACTION PRODUCT OF PHOSPHORUS PENTASULFIDE AND A DICYCLIC TERPENE. 